JP2017065017A - Transfer foil - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transfer foil which can impart sufficient hard coat performance onto the surface of a body to be transferred, prevents transfer failure such as tailing and burrs, and has excellent peeling stability.SOLUTION: There is provided a transfer foil which has at least a base material, a release layer provided on the base material, and a protective layer provided on the release layer, where the release layer contains an active ray curing resin and a thermosetting resin, and the protective layer contains an active ray curing resin.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a transfer foil, and more particularly to a transfer foil that has good transferability and can impart sufficient hard coat performance and plasticizer resistance to the surface of a transfer target.

  IC cards such as ID cards such as ID cards and cash cards such as banks have individual information such as face photos, addresses and names recorded on the surface, and security processing is applied to prevent the contents from being forged or altered. Has been. For example, IC cards provided with holograms on the surface are widely distributed. On the surface of such an IC card, a transfer layer is provided using a transfer foil in order to protect recorded information and holograms.

  The transfer foil has a structure in which a transfer layer including a protective layer that can be transferred is provided on a base material. The transfer foil is transferred onto the surface of a transfer target such as an IC card by transferring the transfer layer. Hard coat performance can be imparted to the surface of the transfer body. In addition, since the transfer layer is more easily peeled off from the base material, the transfer efficiency is improved. Therefore, the transfer layer is preferably adhered to the base material with the minimum necessary adhesive force. If the adhesive force between the substrate and the substrate is too weak, a so-called tailing or burr problem occurs in which a transfer layer at a location where transfer is not scheduled is also transferred to the transfer target. In order to solve such a problem, for example, by adding a melamine resin or the like to a release layer provided between the base material and the transfer layer, an adhesive force that allows the transfer layer to be appropriately held by the base material is obtained. Application to a transfer foil is performed (for example, see Patent Document 1).

  By the way, since the protective layer provided using transfer foil bears protection of the to-be-transferred body surface, such as an IC card, it is calculated | required that the surface strength of a protective layer is high. Therefore, a protective layer is formed using an actinic ray curable resin that is cured by ultraviolet rays or the like, but when these resins are used to increase the surface hardness of the protective layer, a release layer containing a melamine resin is used. Depending on the actinic ray curable resin used, the adhesive strength between the transfer layer and the substrate may be excessively reduced, or the surface strength of the protective layer may be reduced. There was a problem.

JP 2009-67013 A

  The present inventors have now found that the above-mentioned transfer failure is due to some interaction between the component in the resin used for the protective layer and the melamine resin in the release layer. Based on these findings, the transfer foil is provided with a release layer comprising an actinic ray curable resin and a thermosetting resin, and a protective layer comprising an actinic ray curable resin, thereby enabling tailing and variability. The transfer defects such as the above could be improved, and sufficient hard coat performance could be imparted to the surface of the transferred material. The present invention is based on such knowledge.

  Therefore, an object of the present invention is to provide a transfer foil that can impart sufficient hard coat performance to the surface of a transfer material, and does not cause transfer defects such as tailing and burrs, and has excellent peeling stability. Is to provide.

  According to one aspect of the present invention, there is provided a transfer foil comprising at least a base material, a release layer provided on the base material, and a protective layer provided on the release layer, There is provided a transfer foil in which the release layer comprises an actinic ray curable resin and a thermosetting resin, and the protective layer comprises an actinic ray curable resin.

  In the aspect of the present invention, the blending ratio (in terms of solid content) of the actinic ray curable resin and the thermosetting resin in the release layer is 1: 5 to 1: 0.1 on a mass basis. preferable.

  In the embodiment of the present invention, it is preferable that the actinic ray curable resin contained in the release layer and the protective layer comprises urethane (meth) acrylate having a functional group number of 5 or more and 15 or less as a polymerization component. .

  In the embodiment of the present invention, it is preferable that the actinic ray curable resin contained in the release layer and the protective layer comprises urethane (meth) acrylate as a polymerization component.

  In the aspect of the present invention, it is preferable that a receiving layer is provided on the protective layer.

  In the aspect of the present invention, it is preferable that an adhesive layer is provided between the protective layer and the receiving layer.

  According to the present invention, a transfer foil is provided on a base material, a release layer provided on the base material, comprising an actinic ray curable resin and a thermosetting resin, and the release layer. Since it has at least a protective layer comprising an actinic ray curable resin, sufficient hard coat performance and plasticizer resistance can be imparted to the surface of the transfer object, and transfer defects occur in the transfer layer. Can be transferred without any problem.

It is a cross-sectional schematic diagram of the transfer foil by one Embodiment of this invention. It is a cross-sectional schematic diagram of the transfer foil by one Embodiment of this invention. It is a cross-sectional schematic diagram of the transfer foil by one Embodiment of this invention.

<Definition>
In the present specification, “part”, “%”, “ratio” and the like indicating the composition are based on mass unless otherwise specified. “PET” is an abbreviation, synonym, functional expression, common name, or industry term for “polyethylene terephthalate”. The actinic ray curable resin means a precursor or a composition before irradiation with actinic rays, and an actinic ray curable resin is obtained by curing an actinic ray curable resin by irradiating actinic rays. To do. The thermosetting resin means a precursor or a composition before heating, and a thermosetting resin obtained by heating and curing the thermosetting resin is referred to as a thermosetting resin. Further, “(meth) acryl” means “acryl and / or methacryl”, and “(meth) acrylate” means “acrylate and / or methacrylate”.

  In the present specification, the actinic ray means radiation that chemically acts on the actinic ray curable resin to promote polymerization, and specifically, visible light, ultraviolet ray, X-ray, electron beam. , Α ray, β ray, γ ray and the like.

<Transfer foil>
The transfer foil according to the present invention will be described in detail with reference to the drawings. FIG. 1 is a schematic cross-sectional view of a transfer foil according to an embodiment of the present invention. As shown in FIG. 1, the transfer foil 1 according to the present invention includes at least a base material 10, a release layer 20, and a protective layer 30 on the base material 10. According to one embodiment, as shown in FIG. 2, the transfer foil 1 may be provided with an adhesive layer 40 on the protective layer 30. As will be described later, the adhesive layer can also serve as a receiving layer by adjusting its configuration. However, as shown in FIG. 3, the adhesive layer 40 and the receiving layer 50 are provided on the protective layer 30. It may be provided. When the transfer foil 1 is used to transfer to a transfer target (not shown), the protective layer 30 (when the adhesive layer 40 and the receiving layer 50 are provided, the protective layer 30, the adhesive layer 40, and / or the receiving layer 50). ) Is transferred to the transfer medium as the transfer layer 60. Hereinafter, each layer which comprises the transfer foil by this invention is demonstrated.

<Base material>
As a base material, it has heat resistance that can withstand thermal energy (for example, heat of a thermal head) when transferring a transfer layer from a transfer foil to a transfer target, and mechanical strength and solvent resistance that can support the transfer layer. Can be used without particular limitation. For example, polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene terephthalate-isophthalate copolymer, terephthalic acid-cyclohexanedimethanol-ethylene glycol copolymer, polyethylene terephthalate / polyethylene naphthalate coextruded film Polyamide resins such as nylon 6 and nylon 66, polyolefin resins such as polyethylene, polypropylene and polymethylpentene, vinyl resins such as polyvinyl chloride, acrylic resins such as polyacrylate, polymethacrylate and polymethyl methacrylate Imide resins such as polyimide and polyetherimide, polyarylate, polysulfone, polyethersulfone, polyphenylene Engineering resins such as nylene ether, polyphenylene sulfide (PPS), polyaramid, polyether ketone, polyether nitrile, polyether ether ketone, polyether sulfite, and styrenes such as polycarbonate, polystyrene, high impact polystyrene, AS resin, ABS resin Resin, cellophane, cellulose acetate, cellulose film such as nitrocellulose, and the like.

  The base material may be a copolymer resin or a mixture (including an alloy) containing the above-mentioned resin as a main component, or a laminate composed of a plurality of layers. Moreover, although a base film may be a stretched film or an unstretched film, it is preferable to use a film stretched in a uniaxial direction or a biaxial direction for the purpose of improving strength. The base material is used as a film, sheet or board comprising at least one layer of these resins. Among the base materials made of the above-mentioned resins, polyester films such as polyethylene terephthalate and polyethylene naphthalate are preferably used because of their excellent heat resistance and mechanical strength, and among these, polyethylene terephthalate films are more preferable.

  Moreover, an unevenness | corrugation can be provided to the base-material surface as needed for blocking prevention. Examples of means for forming irregularities on the substrate include matting agent kneading, sandblasting, hairline processing, mat coating, or chemical etching. In the case of mat coating, either organic or inorganic materials may be used.

  The thickness of the substrate is preferably 0.5 μm or more and 50 μm or less, and more preferably 4 μm or more and 20 μm or less. When the thickness of the substrate is within the above numerical range, high mechanical strength and transferability can be realized.

  As will be described later, a release layer is provided on the surface of the base material, so that the surface on which the release layer is provided in advance is corona discharge treatment, plasma treatment, ozone treatment, flame treatment, primer (anchor coating, adhesion promotion). (Also referred to as an agent or an easy-adhesive agent) An easy-adhesion treatment such as coating treatment, pre-heat treatment, dust removal treatment, vapor deposition treatment, alkali treatment, or application of an antistatic layer may be performed. Moreover, you may add additives, such as a filler, a plasticizer, a coloring agent, and an antistatic agent, to a base material as needed.

<Release layer>
Next, the release layer provided in the transfer foil according to the present invention will be described. The release layer provided on the base material is a layer for peeling the transfer layer provided on these layers from the transfer foil and transferring it to the transfer target, an actinic ray curable resin, a thermosetting resin, , Comprising. When releasing the transfer layer from the transfer foil, the release layer stays on the substrate side.

  The actinic ray curable resin appropriately contains a polymer, prepolymer, oligomer and / or monomer having a polymerizable unsaturated bond such as (meth) acryloyl group and (meth) acryloyloxy group or an epoxy group in the molecule as a polymerization component. It is preferable to comprise a mixed composition or the like.

  The actinic ray curable resin forming the release layer preferably contains urethane (meth) acrylate, particularly polyfunctional urethane (meth) acrylate, as a polymerization component. When the release layer contains polyfunctional urethane (meth) acrylate, the solvent resistance can be improved. The number of functional groups of the polyfunctional urethane (meth) acrylate is preferably 5 or more and 15 or less, and more preferably 6 or more and 15 or less. The polyfunctional urethane (meth) acrylate is preferably contained in an amount of 10% by mass or more and 90% by mass or less, and more preferably 50% by mass or more and 85% by mass or less, based on the total solid content of the release layer. . The functional group includes, for example, a group having an unsaturated double bond such as a vinyl group.

  Urethane (meth) acrylates include, for example, ethylene glycol, adipic acid, tolylene diisocyanate, 2-hydroxyethyl acrylate, polyethylene glycol, tolylene diisocyanate, 2-hydroxyethyl acrylate, hydroxyethyl phthalyl methacrylate, xylene diisocyanate, 1, 2 -It can be obtained by introducing (meth) acrylic acid into urethane resin such as polybutadiene glycol, tolylene diisocyanate, 2-hydroxyethyl acrylate, trimethylolpropane, propylene glycol, tolylene diisocyanate, 2-hydroxyethyl acrylate. .

  In addition, from the viewpoint of compatibility between solvent resistance and flexibility, the urethane (meth) acrylate having a functional group number of 2 or more and 4 or less and / or (meth) acrylate having a functional group number of 2 or more and 5 or less, It is preferable to contain in combination with a polyfunctional urethane (meth) acrylate. The urethane (meth) acrylate and (meth) acrylate having a functional group number of 2 or more and 5 or less are preferably contained in a total amount of 10% by mass or more and 90% by mass or less based on the total solid content of the release layer. More preferably, it is 50 mass% or more and 85 mass% or less.

  Further, the mass average molecular weights of the polyfunctional and urethane (meth) acrylates having a functional group number of about 2 or more and 4 or less are both preferably 400 or more and 20000 or less, more preferably 500 or more and 10,000 or less. . If the mass average molecular weight of the urethane (meth) acrylate is within the above numerical range, the wear resistance can be improved. Moreover, favorable foil cutting property is realizable by making molecular weight into 20000 or less. For the same reason, the mass average molecular weight of the (meth) acrylate having a functional group number of about 2 or more and 5 or less is preferably in the range of 200 or more and 5000 or less. In the present invention, “mass average molecular weight” means a value measured by gel permeation chromatography using polystyrene as a standard substance, and can be measured by a method based on JIS-K-7252-1.

  Moreover, the actinic ray curable resin forming the release layer may contain an unsaturated bond-containing (meth) acrylate copolymer as a polymerization component. Examples of unsaturated bond-containing (meth) acrylate copolymers include adipic acid, trimellitic acid, maleic acid, phthalic acid, terephthalic acid, hymic acid, malonic acid, succinic acid, glutaric acid, itaconic acid, pyromellitic acid , Fumaric acid, glutaric acid, pimelic acid, sebacic acid, dodecanoic acid, tetrahydrophthalic acid and other polybasic acids, ethylene glycol, propylene glycol, diethylene glycol, propylene oxide, 1,4-butanediol, triethylene glycol, tetra Polyester obtained by the coupling of polyhydric alcohols such as ethylene glycol, polyethylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, 1,6-hexanediol, 1,2,6-hexanetriol (medium ) Polyester (meth) acrylates with acrylic acid introduced, such as bisphenol A, epichlorohydrin, (meth) acrylic acid, phenol novolac, epichlorohydrin, (meth) acrylic acid, (meth) acrylic acid introduced into epoxy resin Examples include epoxy (meth) acrylates, melamine (meth) acrylates, and triazine (meth) acrylates.

  The actinic ray curable resin forming the release layer may contain the following prepolymer, oligomer and / or monomer as a polymerization component in addition to the unsaturated bond-containing acrylic copolymer.

  Examples of the prepolymer include silicone resin acrylates such as polysiloxane (meth) acrylate, polysiloxane diisocyanate, 2-hydroxyethyl (meth) acrylate, and other alkyds in which a (meth) acryloyl group is introduced into an oil-modified alkyd resin. Examples include modified (meth) acrylates and spirane resin acrylates.

  The monomer or oligomer is generally known as an actinic ray polymerizable monomer / oligomer, for example, an acrylate ester compound or a methacrylic ester compound having an ethylenic double bond, and these compounds are It has at least a methacryloyl group or an acryloyl group. For example, 2-ethylhexyl acrylate, 2-hydroxypropyl acrylate, glycerol acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, nonylphenoxyethyl acrylate, tetrahydrofurfuryloxyethyl acrylate, tetrahydrofurfuryloxyhexanolide acrylate, 1,3- Acrylates of ε-caprolactone adduct of dioxane alcohol, monofunctional acrylic acid esters such as 1,3-dioxolane acrylate, or methacrylic acid, itaconic acid, crotonic acid in which these acrylates are replaced with methacrylate, itaconate, crotonate, maleate, Maleate esters such as ethylene glycol diacrylate, triethylene glycol diacrylate , Pentaerythritol diacrylate, hydroquinone diacrylate, resorcin diacrylate, hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate of hydroxypivalate, diacrylate of neopentyl glycol adipate, Diacrylate of ε-caprolactone adduct of neopentyl glycol hydroxypivalate, 2- (2-hydroxy-1,1-dimethylethyl) -5-hydroxymethyl-5-ethyl-1,3-dioxane diacrylate, tricyclo Decane dimethylol acrylate, ε-caprolactone adduct of tricyclodecane dimethylol acrylate, diglycidyl of 1,6-hexanediol Bifunctional acrylic esters such as diter acrylate, or methacrylic acid, itaconic acid, crotonic acid, maleic acid ester in which these acrylates are replaced with methacrylate, itaconate, crotonate, maleate, such as trimethylolpropane triacrylate, ditrimethylol Propane-tetraacrylate, trimethylolethane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, ε-caprolactone adduct of dipentaerythritol hexaacrylate, Pyrogallol triacrylate, propionic acid, dipentaerythri Methacrylate triacrylate, propionic acid / dipentaerythritol tetraacrylate, polyfunctional acrylic acid ester acid such as hydroxypivalylaldehyde-modified dimethylolpropane triacrylate, or methacrylic acid in which these acrylates are replaced with methacrylate, itaconate, crotonate, maleate, Itaconic acid, crotonic acid, maleic acid ester, phosphazene monomer, triethylene glycol, isocyanuric acid EO-modified diacrylate, isocyanuric acid EO-modified triacrylate, dimethylol tricyclodecane diacrylate, trimethylolpropane acrylic acid benzoate, Alkylene glycol type acrylic modified acrylate, modified urethane acrylate not limited to the number of functional groups described above, etc. And the like.

  As thermosetting resin, phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, urea resin, resorcinol resin, furan resin, polyimide resin, polybenzothiazole resin, Examples thereof include amino alkyd resins, melamine / urea cocondensation resins, silicon resins, and polysiloxane resins.

  The content of the actinic ray curable resin in the release layer is preferably 10% by mass or more and 90% by mass or less, and preferably 50% by mass or more and 85% by mass or less with respect to the total solid content of the release layer. Is more preferable. When the content of the actinic ray curable resin is within the above numerical range, transferability can be improved. Further, the content of the thermosetting resin is preferably 8% by mass or more and 40% by mass or less, and more preferably 10% by mass or more and 20% by mass or less, with respect to the total solid content of the release layer. . If the content of the thermosetting resin is within the above numerical range, transferability can be improved. Furthermore, the blending ratio (converted to solid content) of the actinic ray curable resin and the thermosetting resin is preferably 1: 5 to 1: 0.1 on a mass basis, and is 1: 2 to 1: 0.5. It is more preferable that If the blending ratio is within the above numerical range, the transferability of the transfer foil can be improved.

  The release layer preferably contains a photopolymerization initiator and / or a thermal polymerization initiator. The content of the polymerization initiator is preferably 0.1% by mass or more and 5% by mass or less, and preferably 0.5% by mass or more and 4% by mass or less, based on the total solid content of the release layer. More preferably, the content is 1% by mass or more and 3% by mass or less.

  In addition, the release layer can contain a leveling agent, a polymerization terminator, a plasticizer, an antifoaming agent, a silane coupling agent, a lubricant, and the like as additives. Examples of the leveling agent include polyoxyalkylene surfactants, fatty acid ester surfactants, vinyl polymers, and the like.

  For example, the release layer may be formed by applying a coating liquid comprising a composition containing an actinic ray curable resin and a thermosetting resin as described above to a roll coat, reverse roll coat, gravure coat, reverse gravure coat, bar coat, rod. By a known means such as a coat, it is applied onto a substrate to form a coating film, irradiated with ultraviolet rays, the actinic ray curable resin is cured, and then heated and dried at a temperature of about 80 ° C. to 200 ° C. It can be formed by curing a curable resin. For the irradiation of ultraviolet rays, a conventionally known ultraviolet irradiation device can be used, and various types such as a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, a metal halide lamp, an electrodeless ultraviolet lamp, and an LED can be used without limitation. it can. For the electron beam irradiation, either a high energy electron beam irradiation apparatus that irradiates an electron beam with an energy of 100 keV or more and 300 keV or less, or a low energy electron beam irradiation apparatus that irradiates an electron beam with an energy of 100 keV or less is used. The irradiation method may be either a scanning type or a curtain type irradiation device.

Usually, the release layer has a solid content coating amount of preferably 0.1 or more and 5 g / m ² or less, more preferably 0.3 g / m ² or more and 3 g / m ² or less. More preferably, it is 5 g / m ² or more and 1.5 g / m ² or less. If the coating amount is within the above numerical range, the transferability of the transfer foil can be improved.

<Protective layer>
Next, the protective layer will be described. A protective layer bears protection of the to-be-transferred material surface, and comprises actinic-light curable resin.

  The actinic ray curable resin appropriately contains a polymer, prepolymer, oligomer and / or monomer having a polymerizable unsaturated bond such as (meth) acryloyl group and (meth) acryloyloxy group or an epoxy group in the molecule as a polymerization component. It is preferable to comprise a mixed composition or the like.

  The actinic ray curable resin forming the protective layer preferably contains urethane (meth) acrylate, particularly polyfunctional urethane (meth) acrylate, as a polymerization component, like the release layer. When the protective layer contains polyfunctional urethane (meth) acrylate, the solvent resistance can be improved. The number of functional groups of the polyfunctional urethane (meth) acrylate is preferably 5 or more and 15 or less, and more preferably 6 or more and 15 or less. The polyfunctional urethane (meth) acrylate is preferably contained in an amount of 5% by mass or more and 80% by mass or less, more preferably 10% by mass or more and 50% by mass or less, based on the total solid content of the protective layer. The functional group includes, for example, a group having an unsaturated double bond such as a vinyl group.

  Urethane (meth) acrylates include, for example, ethylene glycol, adipic acid, tolylene diisocyanate, 2-hydroxyethyl acrylate, polyethylene glycol, tolylene diisocyanate, 2-hydroxyethyl acrylate, hydroxyethyl phthalyl methacrylate, xylene diisocyanate, 1, 2 -It can be obtained by introducing (meth) acrylic acid into urethane resin such as polybutadiene glycol, tolylene diisocyanate, 2-hydroxyethyl acrylate, trimethylolpropane, propylene glycol, tolylene diisocyanate, 2-hydroxyethyl acrylate. .

  In addition, from the viewpoint of compatibility between solvent resistance and flexibility, the urethane (meth) acrylate having a functional group number of 2 or more and 4 or less and / or (meth) acrylate having a functional group number of 2 or more and 5 or less, It is preferable to contain a urethane (meth) acrylate having a polyfunctional number in combination. The urethane (meth) acrylate and (meth) acrylate having a functional group number of 2 or more and 5 or less are preferably contained in a total amount of 5% by mass or more and 80% by mass or less based on the total solid content of the protective layer. More preferably, it is 10 mass% or more and 70 mass% or less.

  Further, the mass average molecular weights of the polyfunctional and urethane (meth) acrylates having a functional group number of about 2 or more and 4 or less are both preferably 400 or more and 20000 or less, more preferably 500 or more and 10,000 or less. . If the mass average molecular weight of the urethane (meth) acrylate is within the above numerical range, the wear resistance can be improved. Moreover, favorable foil cutting property is realizable by making molecular weight into 20000 or less. For the same reason, the mass average molecular weight of the (meth) acrylate having a functional group number of about 2 or more and 5 or less is preferably in the range of 200 or more and 5000 or less. In the present invention, “mass average molecular weight” means a value measured by gel permeation chromatography using polystyrene as a standard substance, and can be measured by a method based on JIS-K-7252-1.

  Moreover, the actinic ray curable resin forming the protective layer may contain an unsaturated bond-containing (meth) acrylate copolymer as a polymerization component. Examples of unsaturated bond-containing (meth) acrylate copolymers include adipic acid, trimellitic acid, maleic acid, phthalic acid, terephthalic acid, hymic acid, malonic acid, succinic acid, glutaric acid, itaconic acid, pyromellitic acid , Fumaric acid, glutaric acid, pimelic acid, sebacic acid, dodecanoic acid, tetrahydrophthalic acid and other polybasic acids, ethylene glycol, propylene glycol, diethylene glycol, propylene oxide, 1,4-butanediol, triethylene glycol, tetra Polyester obtained by the coupling of polyhydric alcohols such as ethylene glycol, polyethylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, 1,6-hexanediol, 1,2,6-hexanetriol (medium ) Polyester (meth) acrylates with acrylic acid introduced, such as bisphenol A, epichlorohydrin, (meth) acrylic acid, phenol novolac, epichlorohydrin, (meth) acrylic acid, (meth) acrylic acid introduced into epoxy resin Examples include epoxy (meth) acrylates, melamine (meth) acrylates, and triazine (meth) acrylates.

  The actinic ray curable resin forming the protective layer may contain the following prepolymer, oligomer and / or monomer as a polymerization component in addition to the unsaturated bond-containing acrylic copolymer.

  Examples of the prepolymer include silicone resin acrylates such as polysiloxane (meth) acrylate, polysiloxane diisocyanate, 2-hydroxyethyl (meth) acrylate, and other alkyds in which a (meth) acryloyl group is introduced into an oil-modified alkyd resin. Examples include modified (meth) acrylates and spirane resin acrylates.

  The monomer or oligomer is generally known as an actinic ray polymerizable monomer / oligomer, for example, an acrylate ester compound or a methacrylic ester compound having an ethylenic double bond, and these compounds are It has at least a methacryloyl group or an acryloyl group. For example, 2-ethylhexyl acrylate, 2-hydroxypropyl acrylate, glycerol acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, nonylphenoxyethyl acrylate, tetrahydrofurfuryloxyethyl acrylate, tetrahydrofurfuryloxyhexanolide acrylate, 1,3- Acrylates of ε-caprolactone adduct of dioxane alcohol, monofunctional acrylic acid esters such as 1,3-dioxolane acrylate, or methacrylic acid, itaconic acid, crotonic acid in which these acrylates are replaced with methacrylate, itaconate, crotonate, maleate, Maleate esters such as ethylene glycol diacrylate, triethylene glycol diacrylate , Pentaerythritol diacrylate, hydroquinone diacrylate, resorcin diacrylate, hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate of hydroxypivalate, diacrylate of neopentyl glycol adipate, Diacrylate of ε-caprolactone adduct of neopentyl glycol hydroxypivalate, 2- (2-hydroxy-1,1-dimethylethyl) -5-hydroxymethyl-5-ethyl-1,3-dioxane diacrylate, tricyclo Decane dimethylol acrylate, ε-caprolactone adduct of tricyclodecane dimethylol acrylate, diglycidyl of 1,6-hexanediol Bifunctional acrylic esters such as diter acrylate, or methacrylic acid, itaconic acid, crotonic acid, maleic acid ester in which these acrylates are replaced with methacrylate, itaconate, crotonate, maleate, such as trimethylolpropane triacrylate, ditrimethylol Propane-tetraacrylate, trimethylolethane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, ε-caprolactone adduct of dipentaerythritol hexaacrylate, Pyrogallol triacrylate, propionic acid, dipentaerythri Methacrylate triacrylate, propionic acid / dipentaerythritol tetraacrylate, polyfunctional acrylic acid ester acid such as hydroxypivalylaldehyde-modified dimethylolpropane triacrylate, or methacrylic acid in which these acrylates are replaced with methacrylate, itaconate, crotonate, maleate, Itaconic acid, crotonic acid, maleic acid ester, phosphazene monomer, triethylene glycol, isocyanuric acid EO-modified diacrylate, isocyanuric acid EO-modified triacrylate, dimethylol tricyclodecane diacrylate, trimethylolpropane acrylic acid benzoate, Alkylene glycol type acrylic modified acrylate, modified urethane acrylate not limited to the number of functional groups described above, etc. And the like.

  The content of the actinic ray curable resin in the protective layer is preferably 1% by mass or more and 90% by mass or less, and preferably 10% by mass or more and 80% by mass or less, with respect to the total solid content of the release layer. More preferably, it is 30 mass% or more and 70 mass% or less. If content of actinic-light curable resin is in the said numerical range, the transferability of transfer foil can be improved.

  Moreover, it is preferable that a protective layer contains a photoinitiator. It is preferably 0.1% by mass or more and 5% by mass or less, more preferably 0.5% by mass or more and 4% by mass or less, and further preferably 1% by mass or more and 3% by mass or less. .

  The protective layer may contain a filler in addition to the above-described resin. In the present invention, the exposure as described later can improve both the peeling stability and durability of the transfer foil, but since the breaking strength of the protective layer is improved, the protective layer has a certain thickness. If it has, the transfer layer is not easily peeled off from the substrate, and the transfer efficiency of the transfer layer is deteriorated, transfer failure occurs, and peeling stability tends to be lowered. By including a filler in the protective layer, even if the thickness of the protective layer exceeds 20 μm, the breakability is improved, and both the peeling stability and durability of the transfer foil can be improved.

  The filler contained in the protective layer preferably has an average particle size of 40 nm or less. When the average particle size of the filler is 40 nm or less, the transparency of the protective layer can be maintained. Moreover, it is preferable that the average particle diameter is 10 nm or more. When the average particle diameter of the filler is 10 nm or more, the dispersibility can be maintained and the stability of the protective layer coating solution can be maintained. The “average particle size” means the volume average particle size and is measured by a known method using a particle size distribution / particle size distribution measuring device (for example, Nanotrack particle size distribution measuring device, manufactured by Nikkiso Co., Ltd.). can do.

  Examples of the filler include inorganic fillers such as organic fillers, carbon black, graphite, and microsilica, and organic-inorganic hybrid fillers. The filler may be a powder or a sol. From the viewpoint of dispersibility, inorganic particles are preferable among the fillers described above.

  Examples of the inorganic particles include metal oxide particles such as silica particles (colloidal silica, fumed silica, precipitated silica, etc.), alumina particles, zirconia particles, titania particles, and zinc oxide particles. From this viewpoint, it is preferable to use silica particles. Furthermore, it is preferable that the inorganic particles have been subjected to a surface treatment using a silane coupling agent such as γ-aminopropyltriethoxysilane or γ-methacryloxypropyltrimethoxysilane.

  The filler is preferably contained in an amount of 5% by mass or more and 60% by mass or less based on the total solid content of the protective layer. When the content of the filler is within the above numerical range, the transferability of the transfer foil and the abrasion resistance of the printed matter obtained using this transfer foil can be improved, and the protective layer becomes brittle and cracks, etc. It is possible to prevent the occurrence of defects.

  The thickness of the protective layer is preferably 5 μm or more and 20 μm or less. By setting the thickness of the protective layer within the above numerical range, high durability can be imparted while preventing transfer failure.

  The protective layer is a coating solution comprising a composition containing an actinic ray curable resin as described above, by known means such as roll coating, reverse roll coating, gravure coating, reverse gravure coating, bar coating, rod coating, It can form by apply | coating on an intermediate | middle layer, forming a coating film, and making it harden | cure with actinic light. For example, a conventionally known ultraviolet irradiation device can be used for ultraviolet irradiation, and various types such as a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, a metal halide lamp, an electrodeless ultraviolet lamp, and an LED are used without limitation. be able to. For the electron beam irradiation, either a high energy electron beam irradiation apparatus that irradiates an electron beam with an energy of 100 keV or more and 300 keV or less, or a low energy electron beam irradiation apparatus that irradiates an electron beam with an energy of 100 keV or less is used. The irradiation method may be either a scanning type or a curtain type irradiation device.

<Adhesive layer>
Next, the adhesive layer that the transfer foil according to the present invention includes as desired will be described.
The adhesive layer is provided on the protective layer, and improves the adhesion between the transfer layer and the transfer target. Further, the adhesive layer may serve as a receiving layer in which an image is formed by thermal transfer from a thermal transfer sheet having a color material layer by thermal transfer. Then, the transfer portion of the transfer foil on which the image is formed is transferred to the transfer target, and as a result, a printed matter is formed.

  Examples of the material for forming the adhesive layer include heat-bonding adhesives that are melted or softened by heat, and specifically include ionomer resins, acid-modified polyolefin resins, and ethylene- (meth) acrylic. Acid copolymers, ethylene- (meth) acrylic ester copolymers, polyester resins, polyamide resins, vinyl resins, acrylic and methacrylic (meth) acrylic resins, acrylic ester resins, maleic Acid resins, butyral resins, alkyd resins, polyethylene oxide resins, phenol resins, urea resins, melamine resins, melamine-alkyd resins, cellulose resins, polyurethane resins, polyvinyl ether resins, silicones Resin, rubber resin and the like. These resins are used alone or in combination. Among these, vinyl resins, acrylic resins, butyral resins, and polyester resins are preferable in terms of adhesive strength. More preferred are vinyl resins, (meth) acrylic resins such as ethylene- (meth) ethyl acrylate copolymers, and acrylic ester resins.

  Further, when the adhesive layer serves as a receiving layer, it is preferable to use a resin that can easily accept a heat-transferable colorant such as a sublimation dye or a heat-meltable ink. For example, polyolefin resins, polyvinyl chloride, polyvinyl acetate, vinyl chloride-vinyl acetate polymers, vinyl resins such as ethylene-vinyl acetate copolymers or polyacrylates, polyesters such as PET and polybutylene terephthalate Resin, polystyrene resin, polyamide resin, copolymer resin of olefin such as ethylene or propylene and other vinyl polymer, cellulose resin such as ionomer or cellulose diastase, polycarbonate, etc. can be used. A vinyl chloride-vinyl acetate polymer or polyvinyl chloride is preferred, and a vinyl chloride-vinyl acetate polymer is particularly preferred.

  Usually, the thickness of the adhesive layer is preferably 0.5 μm or more and 10 μm or less, and more preferably 1 μm or more and 3 μm or less.

<Receptive layer>
Next, the receiving layer according to the requirements of the transfer foil according to the present invention will be described.
As described above, the adhesive layer plays a role as a receiving layer by adjusting its configuration, but the transfer foil may include a receiving layer separately. In this case, the receiving layer is provided on the adhesive layer, and an image is formed on the receiving layer by thermal transfer from a thermal transfer sheet having a color material layer. Then, the transfer portion of the transfer foil on which the image is formed is transferred to the transfer target, and as a result, a printed matter is formed.

  For this reason, as a material for forming the receiving layer, the same material as that for forming the adhesive layer can be used when the adhesive layer serves as the receiving layer.

  When the receiving layer is transferred to the transfer medium via an adhesive or the like, the adhesiveness of the receiving layer itself is not necessarily required. However, when the receiving layer is transferred to the transfer target without using an adhesive or the like, it is preferable to form the receiving layer using an adhesive resin material such as vinyl chloride-vinyl acetate copolymer. .

  Usually, the thickness of the receiving layer is preferably 0.5 μm or more and 10 μm or less, and more preferably 1 μm or more and 3 μm or less.

  The receptive layer is a receptive layer coating obtained by adding one or more materials selected from the above-mentioned materials and various additives as necessary, and dissolving or dispersing them in an appropriate solvent such as water or an organic solvent. A liquid can be prepared, and this can be formed by applying and drying by means of a gravure printing method, a screen printing method or a reverse coating method using a gravure plate.

  In the transfer foil of the present invention, it is also possible to further provide the adhesive layer having no function as a receiving layer on the receiving layer.

<Transfer of transfer layer>
As a method for transferring the transfer layer onto the transfer object using the transfer foil according to the present invention, a known transfer method may be used, for example, hot stamping by hot stamping (foil stamping), entire surface or stripe transfer by a hot roll, A known method such as a thermal printer (also referred to as a thermal transfer printer) using a thermal head (thermal printing head) can be applied. Among these, transfer by a hot roll is preferable.

  The material to be transferred is not particularly limited as long as it requires durability such as wear resistance and plasticizer resistance. For example, natural fiber paper, coated paper, tracing paper, heat during transfer, and the like. It may be any plastic film, glass, metal, ceramics, wood, cloth or dye-receptive medium that does not deform. In addition, since an IC card or the like usually requires designability and security, when the transfer foil according to the present invention does not include a receiving layer, a printed layer or A hologram layer or the like is generally provided.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

Example 1
Using a polyethylene terephthalate (PET) film having a thickness of 12 μm as a base material, a release layer coating liquid having the following composition is applied to one surface thereof by gravure coating so that the thickness after drying becomes 1 μm, and dried. Then, using a UV exposure device (Fusion UV, F600V, LH10 lamp, H bulb, reflector is a cold type), ultraviolet rays were irradiated with an integrated exposure amount of 220 mJ / cm ² . Furthermore, heat drying was performed at 110 ° C. for 1 minute to form a release layer. The mixing ratio (converted to solid content) of the actinic ray curable resin and the thermosetting resin was 1: 2 on a mass basis.

In addition, the measurement of the integrated exposure amount was performed using a microcure model MC-2 with a UV illuminance measuring instrument microcure data reader manufactured by Fusion UV Systems Japan.
<Releasing layer coating solution composition A>
Actinic ray curable resin, trifunctional acrylate 3.5 parts (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK ester A-9300)
・ 3.5 parts of bifunctional urethane acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK oligomer UA122-P)
-15 functional urethane acrylate 2.0 parts (made by Shin-Nakamura Chemical Co., Ltd., trade name: NK ester U-15HA)
-Photopolymerization initiator 0.2 parts (Ciba Specialty Chemicals, trade name: Irgacure 184)
Thermosetting resin / epoxy group-containing silicone-modified acrylic resin (solid content 50%) 36 parts (manufactured by Daicel Chemical Industries, Ltd., trade name: Cell Top 226)
Aluminum catalyst (solid content 10%) 0.1 part (Daicel Chemical Industries, Ltd., trade name: Cell Top CAT-A)
・ Toluene 30 parts ・ MEK 20 parts

Next, a protective layer coating solution having the following composition is applied on the formed release layer by gravure coating so that the thickness after drying becomes 6 μm, and after drying, a UV exposure device (Fusion UV) , F600V, LH10 lamp, H bulb, and reflecting mirror were cold type) and irradiated with ultraviolet rays to form a protective layer.
<Protective layer coating solution composition>
・ 20 parts of trifunctional acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK ester A-9300)
・ 20 parts of bifunctional urethane acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK oligomer UA122-P)
・ 10 parts of 15 functional urethane acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK ester U-15HA)
・ Unsaturated bond-containing acrylic copolymer 5 parts (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK ester C24T)
・ Photopolymerization initiator 5 parts (Ciba Specialty Chemicals, trade name: Irgacure 907)
Filler (silica) 40 parts (average particle size 12 nm, manufactured by Nissan Chemical Industries, Ltd., trade name: MEK-AC2140Z)
・ Toluene 200 parts ・ MEK 200 parts

Subsequently, on the protective layer formed as described above, an adhesive layer coating liquid having the following composition is applied by gravure coating so that the thickness after drying is 2 μm, and dried to form an adhesive layer. A transfer foil was obtained.
<Adhesive layer coating solution composition>
・ 95 parts of vinyl chloride-vinyl acetate copolymer (manufactured by Nissin Chemical Industry Co., Ltd., trade name: CNL)
・ Epoxy-modified silicone oil 5 parts (Shin-Etsu Chemical Co., Ltd., trade name: KP-1800U)
・ Toluene 200 parts ・ MEK 200 parts

(Example 2)
In Example 1, a transfer foil was prepared in the same manner as in Example 1 except that the composition of the release layer coating solution was changed to the composition shown below. The mixing ratio of the actinic ray curable resin and the thermosetting resin (in terms of solid content) was 1: 1 on a mass basis <Release Layer Coating Liquid Composition B>
Actinic ray curable resin, trifunctional acrylate 3.5 parts (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK ester A-9300)
・ 3.5 parts of bifunctional urethane acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK oligomer UA122-P)
-15 functional urethane acrylate 2.0 parts (made by Shin-Nakamura Chemical Co., Ltd., trade name: NK ester U-15HA)
-Photopolymerization initiator 0.2 parts (Ciba Specialty Chemicals, trade name: Irgacure 184)
18 parts of thermosetting resin / epoxy group-containing silicone-modified acrylic resin (solid content 50%) (manufactured by Daicel Chemical Industries, Ltd., trade name: Cell Top 226)
Aluminum catalyst (solid content 10%) 0.1 part (Daicel Chemical Industries, Ltd., trade name: Cell Top CAT-A)
・ Toluene 30 parts ・ MEK 20 parts

(Example 3)
In Example 2, a transfer foil was prepared in the same manner as in Example 2 except that the release layer was changed so that the thickness after drying was 0.7 μm.

Example 4
In Example 1, a transfer foil was prepared in the same manner as in Example 1 except that the composition of the release layer coating solution was changed to the composition shown below. The blending ratio (solid content conversion) of the actinic ray curable resin and the thermosetting resin was 1: 0.5 on a mass basis.
<Releasing layer coating solution composition C>
Actinic ray curable resin, trifunctional acrylate 3.5 parts (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK ester A-9300)
・ 3.5 parts of bifunctional urethane acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK oligomer UA122-P)
-15 functional urethane acrylate 2.0 parts (made by Shin-Nakamura Chemical Co., Ltd., trade name: NK ester U-15HA)
-Photopolymerization initiator 0.2 parts (Ciba Specialty Chemicals, trade name: Irgacure 184)
Thermosetting resin / epoxy group-containing silicone-modified acrylic resin (solid content 50%) 9 parts (manufactured by Daicel Chemical Industries, Ltd., trade name: Cell Top 226)
Aluminum catalyst (solid content 10%) 0.1 part (Daicel Chemical Industries, Ltd., trade name: Cell Top CAT-A)
・ Toluene 30 parts ・ MEK 20 parts

(Example 5)
In Example 2, a transfer foil was produced in the same manner as in Example 2 except that an intermediate layer of the following coating solution was provided between the protective layer and the adhesive layer.
<Intermediate layer coating solution composition>
-Polyester resin 3.3 parts (Toyobo Co., Ltd., trade name: Byron 200)
・ 2.7 parts of vinyl chloride-vinyl acetate copolymer (manufactured by Nissin Chemical Industry Co., Ltd., trade name: CNL)
・ Isocyanate curing agent 1.5 parts (trade name: XEL curing agent, manufactured by The Inktec Co., Ltd.)
・ Methyl ethyl ketone / toluene (mass ratio 2/1) 10 parts

(Comparative Example 1)
In Example 1, a transfer foil was prepared in the same manner as in Example 1 except that when the release layer was formed, heat drying for 1 minute at 110 ° C. after ultraviolet irradiation was not performed.

(Comparative Example 2)
A film having a melamine-based resin release layer coated on one side of a 12 μm thick PET film is used as a substrate, and a second release layer coating liquid having the following composition is gravure-coated on the release layer. The coating was applied so that the thickness after drying was 0.3 μm.
Otherwise, a transfer foil was prepared in the same manner as in Example 1.
<Composition of release layer coating solution>
・ Carnauba wax (manufactured by Konishi Co., Ltd., trade name: WE-95, solid content 40%) 2 parts ・ Polyethylene wax (solid content 40%) 7 parts ・ Styrene-butadiene rubber 1 part (manufactured by Nippon Zeon Co., Ltd.) (Trade name: Nipol LX430, average particle size 150 nm, solid content 49%, Tg: 12 ° C.)
・ Pure water / IPA (1: 1) 100 parts

(Comparative Example 3)
In Example 1, a transfer foil was prepared in the same manner as in Example 1 except that the composition of the release layer coating solution was as follows.
<Releasing layer coating solution composition D>
Actinic ray curable resin / trifunctional acrylate 1.5 parts (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK ester A-9300)
・ 1.5 parts of bifunctional urethane acrylate (bifunctional, manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK oligomer UA122-P)
-15 functional urethane acrylate 0.8 part (made by Shin-Nakamura Chemical Co., Ltd., trade name: NK ester U-15HA)
-Photopolymerization initiator 0.1 part (Ciba Specialty Chemicals, trade name: Irgacure 907)
・ Toluene 20 parts ・ MEK 20 parts

(Comparative Example 4)
In Example 1, a transfer foil was prepared in the same manner as in Example 1 except that the composition of the release layer coating solution was as follows.
<Releasing layer coating solution composition E>
Thermosetting resin / epoxy group-containing silicone-modified acrylic resin (solid content 50%) 8 parts (Daicel Chemical Industries, Ltd., trade name: Cell Top 226)
・ Aluminum catalyst (solid content 10%) 0.3 part (Daicel Chemical Industries, Ltd., trade name: Cell Top CAT-A)
・ Toluene 20 parts ・ MEK 20 parts

<Evaluation of transfer foil>
A card substrate having the following material composition was used as a transfer target.
<Composition of card substrate>
Polyvinyl chloride compound (degree of polymerization 800) 100 parts (containing 10% additives such as stabilizers)
White pigment (titanium oxide) 10 parts Plasticizer (DOP) 0.5 parts

  Images were printed on the receiving layers of the transfer foils according to Examples 1 and 2 and Comparative Examples 1 to 4 using HDP5000 (manufactured by FARGO) with HDP5000 (manufactured by FARGO).

  Next, the transfer layer was transferred to the adherend layer of the above-described transfer body using HDP5000 (manufactured by FARGO) at a heat roller surface temperature of 175 ° C. and a speed of 2.3 sec / inch.

<< Evaluation of turbidity >>
Under the above transfer conditions, the transfer layer on the card substrate was visually confirmed, and an evaluation test was performed according to the following evaluation criteria. The evaluation results were as shown in Table 1 below.
○: The transfer layer is transparent. Δ: The transfer layer is slightly white and cloudy, but there is no problem with quality.
X: The transfer layer is white and cloudy

<< Foil breakability test >>
Under the above transfer conditions, confirmation of the foil breakability (tailing) of the transfer layer to the card substrate was performed visually, and an evaluation test was performed according to the following evaluation criteria. The evaluation results were as shown in Table 1 below.
A: No tailing occurs (0.5 mm or less)
○: Trailing hardly occurs (1 mm or less)
Δ: Trailing occurs (1 mm or more and 2 mm or less)
X: Tail is considerably generated (4 mm or more)

<< Transferability test >>
After transferring 100 continuous sheets under the above transfer conditions, the external characteristics of the cards were visually evaluated to determine the number of untransferred cards. The evaluation criteria were as follows. The evaluation results are as shown in Table 1 below.
◎: 0 problematic cards ○: 1-9 problematic cards △: 10-20 problematic cards ×: 20 or more problematic cards

<< Surface Strength Test >>
In accordance with ANSI-INCITS322-2002, 5.9 Surface Abrasion, the wear resistance test of the transfer layer on the card surface is visually observed every predetermined number of cycles, and the following evaluation criteria An evaluation test was conducted. The evaluation results are as shown in Table 1.
A: The image after 1500 cycles is good. ○: The image after 1000 cycles is good. Δ: The image after 1000 cycles is not good, but there is no problem in actual use. Later image is bad

DESCRIPTION OF SYMBOLS 1 Transfer foil 10 Base material 20 Release layer 30 Protective layer 40 Adhesive layer 50 Receiving layer 60 Transfer layer

Claims (6)

A transfer foil comprising at least a base material, a release layer provided on the base material, and a protective layer provided in a peelable manner on the release layer,
The release layer comprises an actinic ray curable resin and a thermosetting resin,
The transfer foil, wherein the protective layer comprises an actinic ray curable resin.   The transfer foil according to claim 1, wherein a mixing ratio (in terms of solid content) of the actinic ray curable resin and the thermosetting resin in the release layer is 1: 5 to 1: 0.1 on a mass basis.   The transfer foil according to claim 1 or 2, wherein the actinic ray curable resin contained in the release layer and the protective layer comprises urethane (meth) acrylate as a polymerization component.   The actinic ray curable resin contained in the release layer and the protective layer comprises urethane (meth) acrylate having 5 or more and 15 or less functional groups as a polymerization component. The transfer foil according to item.   The transfer foil according to any one of claims 1 to 4, wherein an adhesive layer is further provided on the protective layer.   The transfer foil according to claim 5, wherein an intermediate layer is provided between the protective layer and the adhesive layer.

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